CN115010102B - Preparation method of difluoro sulfimide - Google Patents
Preparation method of difluoro sulfimide Download PDFInfo
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- CN115010102B CN115010102B CN202210748566.7A CN202210748566A CN115010102B CN 115010102 B CN115010102 B CN 115010102B CN 202210748566 A CN202210748566 A CN 202210748566A CN 115010102 B CN115010102 B CN 115010102B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- XPVRBHCXMWRJEY-UHFFFAOYSA-N difluoro(imino)-$l^{4}-sulfane Chemical compound FS(F)=N XPVRBHCXMWRJEY-UHFFFAOYSA-N 0.000 title claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- -1 amine salt Chemical class 0.000 claims abstract description 50
- 150000001412 amines Chemical class 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims abstract description 14
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- 239000012266 salt solution Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000012074 organic phase Substances 0.000 claims abstract description 9
- 239000012535 impurity Substances 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000011259 mixed solution Substances 0.000 claims abstract 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 6
- 150000003512 tertiary amines Chemical class 0.000 claims description 6
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 3
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical group ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 claims description 3
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical group FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 claims description 3
- ATMIHASMQFJNLZ-UHFFFAOYSA-N dichloro(imino)-$l^{4}-sulfane Chemical compound ClS(Cl)=N ATMIHASMQFJNLZ-UHFFFAOYSA-N 0.000 claims description 2
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 claims description 2
- 150000003141 primary amines Chemical class 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 150000003335 secondary amines Chemical class 0.000 claims description 2
- RKBCYCFRFCNLTO-UHFFFAOYSA-N triisopropylamine Chemical compound CC(C)N(C(C)C)C(C)C RKBCYCFRFCNLTO-UHFFFAOYSA-N 0.000 claims description 2
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 150000003949 imides Chemical class 0.000 claims 3
- 238000003682 fluorination reaction Methods 0.000 abstract description 7
- 229910021645 metal ion Inorganic materials 0.000 abstract description 4
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 abstract description 3
- 238000006138 lithiation reaction Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000005406 washing Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 12
- 150000003863 ammonium salts Chemical class 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 4
- 239000012025 fluorinating agent Substances 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- BRCWHGIUHLWZBK-UHFFFAOYSA-K bismuth;trifluoride Chemical compound F[Bi](F)F BRCWHGIUHLWZBK-UHFFFAOYSA-K 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 229910001512 metal fluoride Inorganic materials 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- ODNBVEIAQAZNNM-UHFFFAOYSA-N 1-(6-chloroimidazo[1,2-b]pyridazin-3-yl)ethanone Chemical compound C1=CC(Cl)=NN2C(C(=O)C)=CN=C21 ODNBVEIAQAZNNM-UHFFFAOYSA-N 0.000 description 1
- GUNJVIDCYZYFGV-UHFFFAOYSA-K Antimony trifluoride Inorganic materials F[Sb](F)F GUNJVIDCYZYFGV-UHFFFAOYSA-K 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910017855 NH 4 F Inorganic materials 0.000 description 1
- CQXADFVORZEARL-UHFFFAOYSA-N Rilmenidine Chemical compound C1CC1C(C1CC1)NC1=NCCO1 CQXADFVORZEARL-UHFFFAOYSA-N 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- JHRWWRDRBPCWTF-OLQVQODUSA-N captafol Chemical compound C1C=CC[C@H]2C(=O)N(SC(Cl)(Cl)C(Cl)Cl)C(=O)[C@H]21 JHRWWRDRBPCWTF-OLQVQODUSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- PQIOSYKVBBWRRI-UHFFFAOYSA-N methylphosphonyl difluoride Chemical group CP(F)(F)=O PQIOSYKVBBWRRI-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/086—Compounds containing nitrogen and non-metals and optionally metals containing one or more sulfur atoms
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of inorganic synthesis, and particularly relates to a preparation method of difluoro sulfimide, which comprises the following steps: mixing the dichloro-sulfonyl-imide with organic amine salt in an organic solvent to obtain a mixed solution, and reacting to obtain a dichloro-sulfonyl-imide organic amine salt solution; adding liquid hydrogen fluoride into the obtained dichloro-sulfonyl-imide organic amine salt solution to obtain a mixed solution, and reacting to obtain a difluoro-sulfonyl-imide organic amine salt solution; filtering the obtained difluoro sulfonimide organic amine salt solution, then extracting to remove impurities, and removing the organic solvent from the obtained organic phase to obtain the difluoro sulfonimide organic amine salt. The bis-fluorosulfonyl imide salt prepared in the patent can be used for removing chlorosulfonic acid in reaction raw materials in a simple water washing mode, and the adopted organic amine salt is also easy to remove in the subsequent lithiation salification process. Meanwhile, as hydrogen fluoride is directly adopted for fluorination, the introduction of metal ions is avoided.
Description
Technical Field
The invention belongs to the technical field of inorganic synthesis, and particularly relates to a preparation method of difluoro sulfimide.
Background
In the particular field of lithium ion batteries, the currently most commonly used electrolyte is lithium hexafluorophosphate (LiPF 6 ) But it has many disadvantages such as low thermal stability, sensitivity to water, and low battery safety. Recently, FSO having fluorosulfonyl group has been studied 2 And exhibit many advantages such as better ionic conductivity and hydrolysis resistance. Inorganic salts of bis-fluorosulfonyl imide, especially lithium bis-fluorosulfonyl imide (LiFSI), have advantages over other fluorine compounds due to their high thermal stability, high electrical conductivity and low corrosiveness. The inorganic salt of the difluoro-sulfonyl imide is prepared into the corresponding difluoro-sulfonyl imide or the organic salt thereof by the fluorination of the dichloro-sulfonyl imideThen reacts with alkali metal compound to prepare the catalyst. The bischlorosulfonimide can be prepared by a variety of methods, but regardless of the method used, the bischlorosulfonimide is generally used only after rectification, mainly because monomer residues and side reactions in the reaction have a large influence on the quality of the final fluoride. However, since the bischlorosulfonimide has a higher boiling point, the bischlorosulfonimide is easy to decompose during rectification, and the total yield is affected. Even so, the rectified bis-chlorosulfonimide contains a certain amount of chlorosulfonic acid, and when bis-fluorosulfonimide is produced by a fluorination reagent, the boiling point of the resulting fluorosulfonic acid is relatively close to that of bis-fluorosulfonimide, resulting in difficulty in removal.
When the bischlorosulfonimide is fluorinated by fluoride, the fluoride may be a metal fluoride, such as that of patent CN 101980955 employing group 11 to 15 elements for the fluorination reaction, including zinc fluoride (ZnF) 2 ) Fluorinated ketones (CuF) 2 ) And bismuth fluoride (BiF) 3 ). The patent also discloses the use of arsenic trifluoride (AsF 3 ) Or antimony trifluoride (SBF) 3 ) As a fluorinating agent. However, since the metal element derived from fluoride is likely to cause deterioration of electrolyte properties after being finally carried into LiFSI, when metal fluoride is used as a fluorinating agent, a relatively complicated purification operation is required for removing the remaining metal element.
Although HF can also be used as a fluorinating agent, as described in patent US 7919629, which uses distilled bischlorosulfonimide to react with gaseous hydrogen fluoride, the yield is only 55% at high temperatures of 130 ℃; patent WO2015/012897A1 discloses a process for producing bis-fluorosulfonyl imide from bis-chlorosulfonyl imide using HF, which yields only 80% of bis-fluorosulfonyl imide despite the continued removal of HCl gas produced by the reaction; the CN104925765 patent reports that the bis-chlorosulfonyl imide reacts with hydrogen fluoride under the action of a catalyst to produce bis-fluorosulfonyl imide, but the catalyst still contains a lewis acid containing metal ions, which easily results in the later-prepared LiFSI containing metal ions.
In the prior art a process for the preparation of metal salts of fluorosulfonyl imides in two steps is disclosed, in the first step, bischlorosulfimide with the fluorinating agent ammonium fluoride (NH 4 F) The reaction is carried out to obtain the difluoro sulfonimide ammonium salt, and then the obtained difluoro sulfonimide ammonium salt is reacted with lithium hydroxide to be converted into difluoro sulfonimide lithium; the prior art also discloses the preparation of bischlorosulfonimide ammonium salts by reacting bischlorosulfonimide with ammonium chloride in acetonitrile solvent, followed by hydrofluorination with hydrogen fluoride to the corresponding bisfluorosulfonimide ammonium salts. However, in this reaction, excessive ammonium fluoride and ammonium chloride remaining after the fluorination reaction increase the acidity, turbidity, chloride ion concentration and sulfonic acid anion concentration of the final lithium bis-fluorosulfonyl imide salt, and in addition, the presence of an amino group causes the generation of subsequent macromolecular impurities.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preparation method of the difluoro sulfimide organic amine salt, which has strong operability, is simple and safe.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a process for preparing a bis-fluorosulfonyl imide organic amine salt comprising the steps of:
(1) Mixing the dichloro-sulfonyl-imide with organic amine salt in an organic solvent, adjusting the pH value of the solution to a certain range by adjusting the addition amount of the organic amine, and reacting at a certain temperature to obtain the dichloro-sulfonyl-imide organic amine salt solution;
(2) Slowly adding a certain amount of liquid hydrogen fluoride into the dichloro-sulfonyl-imide organic amine salt solution obtained in the step (1), and reacting at a certain temperature to obtain the difluoro-sulfonyl-imide organic amine salt solution by adjusting the dosage of the organic amine to keep the pH value of the solution within the range described in the step (1);
(3) Filtering the difluoro sulfonimide organic amine salt solution obtained in the step (2), extracting, and removing the organic solvent from the obtained organic phase to obtain the difluoro sulfonimide organic amine salt.
Preferably, the organic amine of step (1) comprises one or more of a primary amine, a secondary amine or a tertiary amine.
Preferably, the organic amine in the step (1) is a tertiary amine; the tertiary amine comprises one or more of trimethylamine, triethylamine, N-ethyldiisopropylamine, tri-N-propylamine, triisopropylamine, tri-N-butylamine, trioctylamine and pyridine;
preferably, in step (1), the pH of the solution is adjusted to between 5 and 10, more preferably between 6 and 8, by adjusting the amount of organic amine added;
preferably, the organic solvent in the step (1) refers to an organic solvent which does not react with the dichlorosulfimide and the organic salt compound thereof, and comprises one or a combination of more of acetonitrile, dichloroethane and dimethyl carbonate;
preferably, in step (1), the temperature of the reaction is-10 to 20 ℃, more preferably-5 to 10 ℃;
preferably, in step (2), the liquid hydrogen fluoride is added in an amount of between 2.0 and 3.0 times, more preferably between 2.2 and 2.6 times the amount of the bischlorosulfonylimide in step 1;
preferably, in the step (2), the reaction temperature is 20-40 ℃;
preferably, in step (3), the salt and other water-soluble impurities are extracted with pure water.
Preferably, the conductivity of the pure water of step (3) is less than 10uS/cm.
Preferably, in the step (3), the organic solvent is removed by vacuum drying.
Advantageous effects
The invention discloses a preparation method of difluoro sulfimide, wherein the difluoro sulfimide salt prepared in the patent can remove chlorosulfonic acid in the reaction raw material by a simple water washing mode, and the adopted organic amine salt is also easy to remove in the subsequent lithiation salt formation process. Meanwhile, as hydrogen fluoride is directly adopted for fluorination, the introduction of metal ions is avoided.
Drawings
Fig. 1: fluorine spectrum of bis-fluorosulfonyl imide triethylamine salt obtained in example 1.
Detailed Description
Hereinafter, the present invention will be described in detail. Before the description, it is to be understood that the terms used in this specification and the appended claims should not be construed as limited to general and dictionary meanings, but interpreted based on the meanings and concepts corresponding to technical aspects of the present invention on the basis of the principle that the inventor is allowed to define terms appropriately for the best explanation. Accordingly, the description set forth herein is merely a preferred example for the purpose of illustration and is not intended to limit the scope of the invention, so that it should be understood that other equivalents or modifications may be made thereto without departing from the spirit and scope of the invention.
The following examples are merely illustrative of embodiments of the present invention and are not intended to limit the invention in any way, and those skilled in the art will appreciate that modifications may be made without departing from the spirit and scope of the invention. Unless otherwise specified, reagents and equipment used in the following examples are commercially available products.
Example 1
A process for preparing a bis-fluorosulfonyl imide organic amine salt comprising the steps of:
(1) A1000 mL four-mouth bottle is provided with mechanical stirring, a constant pressure dropping funnel, a condenser pipe and a nitrogen guide pipe, the four-mouth bottle is placed in a low-temperature circulation cold bath, then 128.5 g dichloro-sulphonyl-imide is added into a reaction bottle at one time, 278 mL dimethyl carbonate is slowly added into the reaction bottle through the constant pressure dropping funnel, after 100 mL dimethyl carbonate is added, stirring is slowly started, and the temperature in the reaction bottle is kept to be not higher than 15 ℃ until the dimethyl carbonate is completely dripped. Then, 142g of triethylamine is slowly added into the reaction flask through a constant pressure dropping funnel under the condition of keeping the low temperature in the reaction flask, the pH value of the solution is adjusted to 6-8, and the corresponding organic ammonium salt of the dichloro-sulphonyl-imide is obtained through reaction.
(2) The temperature in the reaction bottle is reduced to about minus 15 ℃ by a low-temperature circulation cold bath, 26 g anhydrous hydrogen fluoride (the hydrogen fluoride plays a role of fluorination, mainly the organic ammonium salt of the bischlorosulfonimide is fluorinated into the organic ammonium salt of the bisfluorosulfonimide) is slowly added into the reaction bottle, and the temperature in the reaction bottle is kept below minus 5 ℃ when the reaction bottle is added. After the addition is completed, 43g of triethylamine is continuously added into the reaction bottle, the pH value of the solution is adjusted to 6-8, and the temperature in the reaction bottle is slowly increased to 20 ℃ for reaction for 4 hours.
(3) After the reaction was completed, 100 mL pure water (the purpose of adding water is that the solids are dissolved in water) was slowly added to the reaction flask, and then the aqueous phase and the organic phase were separated. The organic phase was washed with pure water 5 times, and then the solvent was removed by distillation under the reduced pressure to give 157g (yield 92.8%) of bis-fluorosulfonyl imide triethylamine salt.
The fluorine spectrum of the obtained bis-fluorosulfonyl imide triethylamine salt is shown in figure 1.
Example 2
A process for preparing a bis-fluorosulfonyl imide organic amine salt comprising the steps of:
(1) A1000 mL four-mouth bottle is provided with mechanical stirring, a constant pressure dropping funnel, a condenser pipe and a nitrogen guide pipe, the four-mouth bottle is placed in a low-temperature circulation cold bath, then 128.5 g dichloro-sulphonyl imide is added into the reaction bottle at one time, 278 mL dichloroethane is slowly added into the reaction bottle through the constant pressure dropping funnel, after 100 mL dimethyl carbonate is added, stirring is slowly started, and the temperature in the reaction bottle is kept to be not higher than 15 ℃ until the dimethyl carbonate is completely dripped. Then, 142g of tri-n-butylamine is slowly added into the reaction flask through a constant pressure dropping funnel under the condition of keeping the low temperature in the reaction flask, the pH value of the solution is adjusted to 6-8, and the corresponding dichloro-sulphonyl-imine organic ammonium salt is obtained through reaction.
(2) The temperature in the reaction flask is reduced to about-15 ℃ by a low-temperature circulating cold bath, and 26 g anhydrous hydrogen fluoride is slowly added into the reaction flask, so that the temperature in the reaction flask is kept below-5 ℃ during the addition. After the addition is completed, 43g of tri-n-butylamine is continuously added into the reaction flask, the pH value of the solution is adjusted to 6-8, and the temperature in the reaction flask is slowly increased to 20 ℃ for reaction for 4 hours.
(3) After the completion of the reaction, 100 mL pure water was slowly added to the reaction flask, followed by separation of the aqueous phase and the organic phase. The organic phase was washed with pure water 5 times, and then the solvent was removed by distillation under the reduced pressure to give 188.2g of bis-fluorosulfonyl imide tri-n-butylamine salt (yield 85.6%).
Example 3
A process for preparing a bis-fluorosulfonyl imide organic amine salt comprising the steps of:
(1) A1000 mL four-mouth bottle is provided with mechanical stirring, a constant-pressure dropping funnel, a condenser pipe and a nitrogen guide pipe, the four-mouth bottle is placed in a low-temperature circulation cold bath, then 128.5 g dichloro-sulphonyl imine is added into the reaction bottle at one time, 278 mL acetonitrile is slowly added into the reaction bottle through the constant-pressure dropping funnel, after 100 mL dimethyl carbonate is added, stirring is slowly started, and the temperature in the reaction bottle is kept to be not higher than 15 ℃ until the dimethyl carbonate is completely dripped. Then, under the condition of keeping the low temperature in the reaction bottle, 142-g N-ethyldiisopropylamine is slowly added into the reaction bottle through a constant pressure dropping funnel, the pH value of the solution is adjusted to 6-8, and the corresponding organic ammonium salt of the dichloro-sulphonyl-imide is obtained through reaction.
(2) The temperature in the reaction flask is reduced to about-15 ℃ by a low-temperature circulating cold bath, and 26 g anhydrous hydrogen fluoride is slowly added into the reaction flask, so that the temperature in the reaction flask is kept below-5 ℃ during the addition. After the addition is completed, 43g N-ethyldiisopropylamine is continuously added into the reaction bottle, the pH value of the solution is adjusted to 6-8, and the temperature in the reaction bottle is slowly increased to 20 ℃ for reaction for 4 hours.
(3) After the completion of the reaction, 100 mL pure water was slowly added to the reaction flask, followed by separation of the aqueous phase and the organic phase. The organic phase was washed with pure water 5 times, and then the solvent was removed by distillation under reduced pressure to obtain bis-fluorosulfonyl imide tri-n-butylamine salt.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be apparent to one skilled in the art that modifications may be made to the technical solutions described in the foregoing embodiments, or equivalents may be substituted for some of the technical features thereof; such modifications and substitutions do not depart from the spirit and scope of the corresponding technical solutions.
Claims (7)
1. The preparation method of the difluoro sulfimide is characterized by comprising the following steps of:
(1) Mixing the dichloro-sulfonyl-imide with organic amine salt in an organic solvent to obtain a mixed solution, and reacting to obtain a dichloro-sulfonyl-imide organic amine salt solution; the organic solvent is an organic solvent which does not react with the dichlorosulfimide and the organic salt compound thereof; the reaction temperature is-10-20 ℃;
(2) Adding liquid hydrogen fluoride into the dichloro sulfonyl imide organic amine salt solution obtained in the step (1) to obtain a mixed solution, and reacting to obtain a difluoro sulfonyl imide organic amine salt solution; the addition amount of the liquid hydrogen fluoride is 2.0-3.0 times of the amount of the dichloro sulfonyl imide in the step 1; the reaction temperature is 20-40 ℃;
(3) Filtering the difluoro sulfonimide organic amine salt solution obtained in the step (2), then extracting to remove impurities, and removing the organic solvent from the obtained organic phase to obtain the difluoro sulfonimide organic amine salt.
2. The method of preparing bis-fluorosulfonyl imide of claim 1, wherein the organic amine of step (1) comprises a combination of one or more of a primary amine, a secondary amine, or a tertiary amine.
3. The method for producing a bis-fluorosulfonyl imide according to claim 2, wherein said organic amine is a tertiary amine; the tertiary amine comprises one or a combination of more of trimethylamine, triethylamine, N-ethyldiisopropylamine, tri-N-propylamine, triisopropylamine, tri-N-butylamine, trioctylamine and pyridine.
4. The method for producing a bis-fluorosulfonyl imide according to claim 1, wherein the organic solvent of step (1) comprises a combination of one or more of acetonitrile, dichloroethane, and dimethyl carbonate.
5. The method for producing a bisfluorosulfonyl imide according to claim 1, wherein in the step (1), the pH of the mixed solution is adjusted to 5 to 10 by adjusting the amount of the organic amine added.
6. The method for producing a bisfluorosulfonyl imide according to claim 5, wherein in step (2), the pH of the mixed solution is maintained between 5 and 10 by adjusting the amount of the organic amine.
7. The process for producing a bisfluorosulfonyl imide according to claim 1, wherein in the step (3), a salt and other water-soluble impurities are extracted with pure water; the conductivity of the pure water is less than 10 uS/cm; and removing the organic solvent by adopting a vacuum drying method.
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